JP2008231617A - Inkjet printing method and printed matter - Google Patents

Abstract

Even if washing is performed together with dirty clothes or easily discolored clothes, a portion of a cationic substance included in a cloth, particularly a region other than an image region, can be selectively stained and stained. Providing an ink jet textile printing method in which a textile print that does not occur is obtained.
In a method for inkjet printing in which inkjet recording is performed on a fabric, inkjet using a pigment ink containing a dispersant having an anionic group and a pigment is applied to a fabric containing at least a thermoplastic resin and a nitrogen-containing cationic substance. A recording step for performing recording, a post-processing step for imparting an anionic compound that binds to the nitrogen-containing cationic substance to the fabric on which inkjet recording has been performed in the step, and inkjet recording after the post-processing step And a heating step of heating and fixing the ink of the fabric that has been rubbed.
[Selection figure] None

Description

  The present invention relates to an inkjet printing method using a pigment ink and a printed matter obtained by the printing method.

  Conventionally, dye ink has been used in a textile printing method using an ink jet recording method. Since there are vivid pigment compounds of various shades in dyes, the use of dye ink has the advantage that a clear pattern with excellent color tone can be displayed on the fabric. However, when a dye ink is used, the fabric must be post-treated by a method corresponding to the dye contained in the dye ink for the purpose of fixing the dye to the fiber after the dyeing step. For this reason, it leads to an increase in the number of processes and costs, and there is a problem that it is necessary to consider productivity problems and environmental pollution, such as the necessity of waste liquid treatment.

  In contrast, when pigment ink is used, the color tone and sharpness are generally inferior to those when dye ink is used, but because the pigment has excellent light resistance and water resistance, printing with good fastness is possible. There is an advantage that things can be obtained. In addition, when pigment ink is used for textile printing using the ink jet recording method, there is an advantage that a complicated post-treatment for the fabric is unnecessary as compared with the case where dye ink is used. For these reasons, an ink-jet textile printing method using a pigment ink has attracted attention at present.

  Incidentally, as a recording medium widely used in the ink jet recording method, a medium having an ink receiving layer containing inorganic fine particles such as silica and alumina and a water-soluble polymer is generally used. The presence of the ink receiving layer improves the quality of the ink jet recorded image. However, when the above-described technique is applied when the recording medium is a fabric, the texture of the fabric is impaired, and the obtained printed matter has an insufficient image density and is poor in washing fastness. Become.

  On the other hand, Patent Document 1 proposes a method in which when a fabric is used as a recording medium, a hydrophobic low molecular weight compound and a cationic resin are applied to the fabric, and then an image is formed using a pigment ink. By using this method, it is said that a high-density printed matter can be obtained without impairing the texture of the fabric. However, according to the study by the present inventors, the printed matter has the following new problems with respect to washing fastness. That is, when the printed matter is washed together with dirty clothes or easily discolored clothes, the stains and dyes may be selectively dyed to the cationic substance used in the above treatment. .

  In Patent Document 2, a nitrogen-containing cationic substance is applied to an image forming region of a fabric, and after inkjet recording using a pigment ink having an anionic group in the region, a thermoplastic hydrophobic resin is applied on the image. An ink jet printing method to be applied is proposed. According to this method, a printed matter having sufficient washing fastness and almost no contamination outside the image formation can be obtained. However, according to the study of the present inventors, it has been found that there is a problem in the washing fastness of the printed material even in this method. In the above method, the nitrogen-containing cationic substance is applied to the image forming area of the fabric. However, when the nitrogen-containing cationic substance is applied to a portion other than the image forming area of the fabric, the same problem as described above occurs. Arise. That is, when a cationic substance is applied to a part other than the image forming area, if the obtained printed matter is washed together with dirty clothes or easily discolored clothes, the dirt or dyeing is applied to this part. Or the like occurs selectively. This means that in order to solve this problem by the above-described method, the application of the nitrogen-containing cationic substance to the fabric must be performed so as to coincide with the image forming area of the fabric. For this reason, there is a concern about a decrease in the yield of products when obtaining a good printed matter by the above method.

JP 2001-140174 A JP 2005-320663 A

  Accordingly, an object of the present invention is to improve the following points in particular in an ink jet textile printing method for performing ink jet recording using a pigment ink on a cloth containing a cationic substance. That is, the present invention provides an ink-jet printing method capable of obtaining a printed material that does not cause partial dyeing, in which stains and dyeing are selectively dyed even on an area other than an image area, in particular, a cationic substance included in a fabric. Objective. Another object of the present invention is to provide the above excellent printed matter obtained by the printing method.

  The above object is achieved by the following means. That is, the present invention uses a pigment ink containing a dispersant having an anionic group and a pigment for a fabric containing at least a thermoplastic resin and a nitrogen-containing cationic substance in an inkjet printing method for performing inkjet recording on the fabric. A recording step for performing inkjet recording, a post-treatment step for imparting an anionic compound that binds to the nitrogen-containing cationic substance to the fabric on which inkjet recording has been performed in the step, and after the post-treatment step, And a heating step of heating and fixing the ink of the fabric on which ink jet recording has been performed.

  Another embodiment of the present invention is a printed matter manufactured by the above-described inkjet printing method of the present invention.

  The present invention relates to an ink jet printing method for performing ink jet recording using a pigment ink on a cloth containing a thermoplastic resin and a nitrogen-containing cationic substance obtained by pretreatment with a pretreatment liquid. Have That is, according to the present invention, even when a cloth containing a cationic substance is used, when the obtained printed matter is washed, stains and dyes are selectively dyed on the cationic substance. Therefore, it is possible to provide a printed material having an excellent texture without causing “partial dyeing”. In addition, according to the present invention, the above-described excellent quality printed matter obtained by the printing method can be economically provided with a high yield.

Hereinafter, the present invention will be described in more detail with reference to the best mode for carrying out the invention. The inkjet textile printing method of the present invention is characterized by having at least each step described below.
(1) A recording step of performing inkjet recording on a fabric containing at least a thermoplastic resin and a nitrogen-containing cationic substance using a pigment ink containing a dispersant having an anionic group and a pigment.
(2) A post-treatment step of imparting an anionic compound that binds to the nitrogen-containing cationic substance to the fabric on which ink jet recording has been performed in the recording step.
(3) A heating step for heat-fixing the ink of the fabric on which ink jet recording has been performed after the post-processing step.

  As described above, in the present invention, first, an ink containing a dispersant having an anionic group and a pigment or a pigment having an anionic group is used for a fabric containing at least a thermoplastic resin and a nitrogen-containing cationic substance. Inkjet recording is performed. A feature of the present invention is that an anionic compound that binds to the nitrogen-containing cationic substance is then imparted to the fabric on which ink jet recording has been performed in a post-processing step. The purpose of imparting the anionic compound to the fabric in the post-treatment step is to cancel the ionicity on the fabric after ink jet recording, so that when the printed matter is washed, the dye or the nitrogen-containing cationic substance the fabric has This is to prevent partial staining such as dirt. In the present invention, the fabric on which ink jet recording has been performed is further heated after the post-processing step, whereby the adhesiveness between the thermoplastic resin and the fabric, the dispersant and the pigment can be improved. Hereinafter, each process is demonstrated in order.

  In the present invention, first, a cloth containing a thermoplastic resin and a nitrogen-containing cationic substance is prepared in advance as a cloth to be printed. Of the fabric, the region containing the thermoplastic resin and the nitrogen-containing cationic substance may, of course, be an image forming region or the entire fabric. As a specific treatment method, the fabric is treated with a pretreatment liquid containing at least a thermoplastic resin and a nitrogen-containing cationic substance, so that the cloth contains the thermoplastic resin and the nitrogen-containing cationic substance. Examples of the treatment method include making the pretreatment liquid water-soluble and applying it to the fabric with a spray, a roller, a brush, or the like. The pretreatment liquid can also be applied to the fabric by an ink jet recording method. Hereinafter, the thermoplastic resin and the nitrogen-containing cationic substance used for the above treatment will be described.

  In the present invention, a fabric containing a thermoplastic resin and a nitrogen-containing cationic substance is used. The fabric can be obtained, for example, by performing the above treatment in advance. Hereinafter, these materials will be described. As the thermoplastic resin, those having a film forming ability capable of softening by heat and then solidifying to form a resin film when the fabric is heated in a heating process for heating and fixing the ink described later are used. Furthermore, a pigment or a dispersant in the ink can be fixed in a good state in the film, and the formed film is rich in flexibility without impairing the texture of the fabric. It is done.

  Suitable thermoplastic resins for application to such fabrics include elastomer emulsions (emulsions) used in normal pigment printing. Examples of the resin include acrylic copolymer resin, polyurethane resin, vinyl acetate resin, and vinyl chloride. Among these, acrylic copolymer resins are particularly preferable. Furthermore, the glass transition temperature of the thermoplastic resin used in the present invention is preferably −35 ° C. or higher and 45 ° C. or lower, and particularly preferably −25 ° C. or higher and 20 ° C. or lower. In the case of a resin having a glass transition temperature of less than -35 ° C, the abrasion resistance of the image of the obtained printed matter may be insufficient. On the other hand, when a resin having a glass transition temperature higher than 45 ° C. is used, the adhesion of the resin coating layer to the fabric and the texture of the fabric may be deteriorated. In addition, the amount of the thermoplastic resin in the fabric needs to be determined based on a balance between sufficient film forming ability and fabric texture. For example, when a pretreatment liquid containing a thermoplastic resin and a nitrogen-containing cationic substance is preliminarily applied to a fabric by spraying or the like, the content of the thermoplastic resin in the pretreatment liquid should be adjusted as follows. Is preferred. Specifically, it is preferable to use a pretreatment liquid in which the content of the thermoplastic resin is 0.5% by mass or more and 7% by mass or less, and further 3% by mass or more and 5% by mass or less. In this case, when the content of the thermoplastic resin in the pretreatment liquid is less than 0.5% by mass, sufficient film forming ability is not exhibited, and the above effects may not be sufficiently obtained. On the other hand, when the content in the pretreatment liquid exceeds 7% by mass, the texture of the fabric may be impaired when the pretreatment liquid is used.

  Examples of the nitrogen-containing cationic substance used in the present invention include a cationic resin containing nitrogen in the structure and a cationic surfactant. Specific examples of the cationic resin include the following. Polyethyleneimine, polyvinyl pyridine, polydialkylaminoethyl methacrylate, polydialkylaminoethyl acrylate, etc. or modified products thereof. Polydialkylaminoethyl methacrylamide, polydialkylaminoethyl acrylamide, polyepoxyamine, polyamidoamine and the like or modified products thereof. Dicyandiamide / formalin condensate, dicyandiamide polyalkyl / polyalkylene polyamine condensate, etc. or modified products thereof. Polydiallyldimethylammonium chloride, polyvinylamine, polyallylamine, acrylamide / diallylamine hydrochloride copolymer, dimethylamine epichlorohydrin polycondensate and the like or modified products thereof. These can be used by appropriately selecting one kind or two or more kinds. Of course, the present invention is not limited to these.

  Specific examples of the cationic surfactant include the following. Primary, secondary or tertiary amine salt type compounds such as hydrochlorides and acetates such as laurylamine, stearylamine or rosinamine. Quaternary ammonium salt type compounds such as lauryltrimethylammonium chloride, lauryldimethylbenzylammonium chloride, cetyltrimethylammonium chloride or benzalkonium chloride. An amphoteric surfactant that exhibits cationic properties in a certain pH range, such as an amino acid-type amphoteric surfactant or a betaine-type compound adjusted to an isoelectric point or lower. These can be used by appropriately selecting one kind or two or more kinds. Of course, the present invention is not limited to these.

  Some of the nitrogen-containing cationic substances listed above are colored and easily discolored. In the present invention, among the above-mentioned nitrogen-containing cationic substances, it is preferable to use those which are colorless and hardly discolored and have high reactivity with the anionic compound used in the post-treatment process described later. Since the quaternary ammonium salt type compound is a nitrogen-containing cationic substance that is colorless and hardly discolored and has high reactivity with an anionic compound, it is particularly suitable for the present invention. The following effects are obtained when ink-jet recording is performed using a dispersant and pigment having an anionic group or a pigment ink containing a pigment having an anionic group on a cloth having a nitrogen-containing cationic substance as described above. It is done. That is, when ink-jet recording is performed on a cloth having a nitrogen-containing cationic substance with any of the above-described inks, the trapping property of the dispersant and pigment having an anionic group or the pigment having an anionic group is improved. be able to. As a result, a printed product having excellent washing fastness at a high concentration can be obtained.

  Further, it is preferable that the amount of the nitrogen-containing cationic substance in the fabric be at least such that the dispersant and the pigment having an anionic group in the ink or the pigment having an anionic group are sufficiently captured. For example, when a pretreatment liquid containing a thermoplastic resin and a nitrogen-containing cationic substance is applied to the fabric in advance by spraying or the like, the content of the nitrogen-containing cationic substance in the pretreatment liquid is adjusted as follows: It is preferable to do. Specifically, the content of the nitrogen-containing cationic substance in the pretreatment liquid is preferably 0.05% by mass to 5% by mass, and more preferably 0.1% by mass to 1% by mass. If the content of the nitrogen-containing cationic substance is less than 0.05% by mass, the above effect may not be sufficiently obtained. On the other hand, even if the content of the nitrogen-containing cationic substance in the pretreatment liquid exceeds 5% by mass, further performance improvement cannot be expected and it is not economical.

  In the present invention, the content of the thermoplastic resin and the nitrogen-containing cationic substance contained in the fabric is such that their mass ratio (thermoplastic resin: nitrogen-containing cationic substance) is 140: 1 to 1:10. It is preferable to make it. That is, the content (mass%) ratio in the pretreatment liquid is preferably (thermoplastic resin content) / (nitrogen-containing cationic substance content) = 0.1 or more and 140 or less. According to the study by the present inventors, the above-described effects of the present invention are remarkably obtained in this case. Therefore, in the treatment of the fabric, it is preferable to use a fabric pretreatment liquid in which the thermoplastic resin and the nitrogen-containing cationic substance are contained in the above range. Further, if necessary, a material obtained by adding other additives such as a pH adjusting agent, a penetrating agent or a crosslinking agent to the fabric pretreatment liquid may be used.

  The method for applying the fabric treatment liquid comprising the above-described components to the fabric may be any known method such as a pad method, a spray method, a printing method, or a coating method, and is not particularly limited. .

  The fabric material used in the present invention may be any conventionally known material. For example, a cloth made of cotton, silk, hemp, rayon, acetate, nylon, or polyester fiber, or a blended cloth made of two or more of these fibers can be used as the material of the cloth.

  In the ink-jet printing method of the present invention, an ink containing a dispersant and a pigment having an anionic group, or a pigment having an anionic group is applied to a fabric containing the above-described thermoplastic resin and a nitrogen-containing cationic substance. Inkjet recording is performed. In the textile printing method of the present invention, an ink having the above-described configuration may be selected from conventionally known ink jet recording methods. For example, an ink containing a pigment containing an anionic group and a pigment having self-dispersibility can be used, but in this case, a dispersant is not necessarily required. In the case of using an ink in which a pigment is dispersed in a liquid medium with a dispersant, an ink in which the pigment is dispersed with a dispersant having a pigment and an anionic group can be used. These inks preferably contain water or a liquid medium containing water and a water-soluble organic solvent for dissolving or dispersing components such as pigments. In addition, the ink used in the present invention may appropriately contain various additives such as a pH adjuster, an antifungal agent, a surfactant, or a resin. Below, each component of the ink used by this invention is demonstrated.

<Ink configuration>
(Ink liquid medium, etc.)
Preferable examples of the water-soluble organic solvent used in the liquid medium include glycols, glycol ethers, nitrogen-containing solvents, and the like. These can be used by appropriately selecting one kind or two or more kinds. Moreover, as a surfactant, the following can be used, for example. Mention may be made of anionic surfactants such as fatty acid salts, higher alcohol sulfates, liquid fatty oil sulfates and alkylallylsulfonates. Further, nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, and polyoxyethylene sorbitan alkyl esters can be mentioned. These surfactants can be used by appropriately selecting one kind or two or more kinds.

(Pigment)
As the pigment, for example, the following can be used. As the pigment used in the black ink, carbon black can be used. Specifically, carbon black such as furnace black, lamp black, acetylene black, or channel black can be used. These can be used by appropriately selecting one kind or two or more kinds. Of course, commercially available carbon blacks as listed below and newly prepared carbon blacks can also be used.

  Ray Van: 7000, 5750, 5250, 5000ULTRA, 3500, 2000, 1500, 1250, 1200, 1190ULTRA-II, 1170, 1255 (above Colombia). Black Pearls L, Legal: 400R, 330R, 660R, Mogul L, Monak: 700, 800, 880, 900, 1000, 1100, 1300, 1400, Vulcan XC-72R (manufactured by Cabot). Color black: FW1, FW2, FW2V, FW18, FW200, S150, S160, S170, Printex: 35, U, V, 140U, 140V, Special Black: 6, 5, 4A, 4 (manufactured by Degussa). No. 25, no. 33, no. 40, no. 47, no. 52, no. 900, no. 2300, MCF-88, MA600, MA7, MA8, MA100 (manufactured by Mitsubishi Chemical).

  Specific examples of organic pigments used in color inks include those listed below. Insoluble azo pigments such as toluidine red, toluidine maroon, Hansa yellow, benzidine yellow and pyrazolone red. Soluble azo pigments such as Ritolol Red, Helio Bordeaux, Pigment Scarlet, and Permanent Red 2B. Derivatives from vat dyes such as alizarin, indanthrone and thioindigo maroon. Phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green. Quinacridone pigments such as quinacridone red and quinacridone magenta. Perylene pigments such as perylene red and perylene scarlet. Isoindolinone pigments such as isoindolinone yellow and isoindolinone orange. Imidazolone pigments such as benzimidazolone yellow, benzimidazolone orange and benzimidazolone red. Pyranthrone pigments such as pyranthrone red and pyranthrone orange. Indigo pigment. Condensed azo pigment. Thioindigo pigment. Diketopyrrolopyrrole pigment. Flavanthrone yellow, acylamide yellow, quinophthalone yellow, nickel azo yellow, copper azomethine yellow, perinone orange, anthrone orange, dianthraquinonyl red or dioxazine violet. These can be used by appropriately selecting one kind or two or more kinds.

  In addition, when the organic pigment is represented by a color index (CI) number, the following can be used. C. I. Pigment Yellow: 12, 13, 14, 17, 20, 24, 74, 83, 86, 93, 97, 109, 110, 117, and the like. In addition, C.I. I. Pigment Yellow: 120, 125, 128, 137, 138, 147, 148, 150, 151, 153, 154, 166, 168, 180, 185 and the like. C. I. Pigment Orange: 16, 36, 43, 51, 55, 59, 61, 71, etc. C. I. Pigment Red: 9, 48, 49, 52, 53, 57, 97, 122, 123, 149, 168, 175, 176, 177, 180, 192, and the like. C. I. Pigment Red: 215, 216, 217, 220, 223, 224, 226, 227, 228, 238, 240, 254, 255, 272, etc. C. I. Pigment violet: 19, 23, 29, 30, 37, 40, 50, and the like. C. I. Pigment Blue: 15, 15: 1, 15: 3, 15: 4, 15: 6, 22, 60, 64, and the like. C. I. Pigment Green: 7, 36, etc. C. I. Pigment Brown: 23, 25, 26, etc.

(Dispersant)
As the dispersant used together with the pigment constituting the ink used in the present invention, those having an anionic group are suitable, and an anionic surfactant or a polymer dispersing agent having an anionic group can be used. For example, it is a polymer dispersant having an anionic group, and specific examples include a styrene-acrylic acid copolymer.

(Pigment having an anionic group)
The pigment having an anionic group constituting the ink used in the present invention is preferably formed by bonding an anionic group to the surface of the pigment particle. Examples of the anionic group include at least one selected from the group consisting of —COOM, —SO ₃ M, and —PO ₃ HM (M in the formula represents a hydrogen atom, an alkali metal, ammonium, or organic ammonium. Represent.) The above-described functional group may be directly bonded to the surface of the pigment particle, or may be chemically bonded through another atomic group. Examples of the other atomic group include an alkylene group having 1 to 12 carbon atoms, a substituted or unsubstituted phenylene group, and a substituted or unsubstituted naphthylene group. Such a self-dispersing carbon black is described in, for example, pamphlet of WO 97/47699. In the present invention, among the above ionic groups, it is particularly preferable to use a pigment in which —COOM is chemically bonded to the surface of the carbon black particle directly or via another atomic group.

<Post-processing step and heating step>
Next, a post-processing step characterizing the ink jet textile printing method of the present invention and a subsequent heating step will be described. In the post-processing step, an anionic compound is imparted to the fabric on which ink jet recording has been performed, and the anionic compound that binds to the nitrogen-containing cationic substance as described above contained in the fabric is used. . As described above, in the present invention, the application of such an anionic compound to the fabric counteracts the ionicity of the fabric, thereby eliminating the problem of partial dyeing that may occur when the printed matter is washed. Resolve. Hereinafter, the anionic compound used in the post-treatment process will be described. As the anionic compound used in the post-treatment step of the present invention, for example, anionic resins and anionic surfactants listed below can be used. Specific examples of the anionic resin that can be used in the present invention include polyacrylic acid or a salt thereof, polymethacrylic acid or a salt thereof, alginic acid or a salt thereof, pectin, a maleic acid copolymer, polyphosphoric acid, or poval sulfate. Can be mentioned. These can be used by appropriately selecting one kind or two or more kinds. Of course, the present invention is not limited to these.

  Specific examples of the anionic surfactant that can be used in the present invention include the following. Alkyl sulfate ester salt, alkylbenzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfosuccinate, alkyl diphenyl ether disulfonate, alkyl phosphate, and the like. Polyoxyethylene alkyl sulfate, polyoxyethylene alkyl allyl sulfate, polyoxyethylene alkyl ether sulfate and the like. Polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene polystyryl phenyl ether sulfate or polyoxyethylene alkyl phosphate. These can be used by appropriately selecting one kind or two or more kinds. Of course, the present invention is not limited to these.

  The anionic compound can also be applied to the fabric as a post-treatment liquid together with water or a liquid medium containing water and a water-soluble organic solvent. The post-treatment liquid may be added with other additives if necessary.

  Examples of the method for applying the anionic compound to the fabric include using a post-treatment liquid having the above-described configuration and applying the same by a known method such as a pad method, a spray method, a printing method, or a coating method. . The post-treatment liquid can also be applied to the fabric by an ink jet recording method. Of course, the present invention is not particularly limited.

  In the ink-jet textile printing method of the present invention, an anionic compound is applied to a fabric on which ink-jet recording has been performed with a pigment ink, and then the ink is heat-fixed in a heating step, which will be described below. The temperature at which the ink applied on the fabric is heated and fixed varies depending on the thermoplastic resin used, but is preferably 100 ° C. or higher and 200 ° C. or lower, more specifically about 150 ° C., for example. The heating time is not particularly limited and is preferably, for example, about 1 minute to 10 minutes, more specifically about 3 to 5 minutes. Further, the machine for heating and fixing the ink on the fabric is not particularly limited, and examples thereof include a pin tenter and a universal press. Furthermore, the ink jet textile printing method of the present invention can include other steps as necessary in addition to the steps described above.

Hereinafter, an ink jet recording method and an ink jet recording apparatus used in the ink jet recording process of the present invention will be described.
<Inkjet recording method and inkjet recording apparatus>
In the ink-jet printing method of the present invention, an image is formed on the fabric described above by the ink-jet recording method using the above-described pigment ink, and then a printed product is obtained through a post-processing step and a heating step. At that time, a desired image is recorded by scanning the recording head of the ink jet recording apparatus on the cloth and applying the ink to a desired position.

  The ink jet recording method and the ink jet recording apparatus may be of any conventionally known recording method. For example, an ink jet recording method and an ink jet recording apparatus that generate ink droplets by applying thermal energy corresponding to a recording signal to ink in a recording head can be used.

Hereinafter, an example of the ink jet recording apparatus will be described. First, FIG. 1 and FIG. 2 show an example of a head configuration which is a main part of an ink jet recording apparatus using thermal energy. FIG. 1 is a cross-sectional view of the head 13 along the ink flow path, and FIG. 2 is a cross-sectional view taken along line AB in FIG. The head 13 is obtained by bonding a heating element substrate 15 and a glass, ceramic, silicon, or plastic plate having a flow path (nozzle) 14 through which ink passes. The heating element substrate 15 is configured by the following (16 to 20). A protective layer 16 formed of silicon oxide, silicon nitride, silicon carbide, or the like. Electrodes 17-1 and 17-2 formed of aluminum, gold, aluminum-copper alloy, or the like. A heating resistor layer 18 formed of a high melting point material such as HfB ₂ , TaN or TaAl. A heat storage layer 19 formed of thermally oxidized silicon or aluminum oxide. A substrate 20 formed of a material having good heat dissipation such as silicon, aluminum, or aluminum nitride.

  Image formation by the recording head 13 having the above-described configuration is performed as follows. First, when a pulsed electric signal is applied to the electrodes 17-1 and 17-2, the region indicated by n of the heating element substrate 15 rapidly generates heat, and bubbles are generated in the ink 21 in contact with the surface. To do. The meniscus 23 protrudes due to the pressure of the bubbles, the ink 21 is ejected through the nozzle 14 of the head 13, becomes an ink droplet 24 from the ejection orifice 22, and flies toward the recording medium 25.

  FIG. 3 is an external view of an example of a multi-head in which a large number of recording heads shown in FIG. 1 are arranged. This multi-head is made by adhering a glass plate 27 having multi-nozzles 26 and a heating head 28 similar to that described in FIG.

  FIG. 4 is a perspective view showing an example of an ink jet recording apparatus incorporating this head. Reference numeral 61 denotes a blade as a wiping member, one end of which is held and fixed by a blade holding member, and forms a cantilever. The blade 61 is disposed at a position adjacent to the recording area by the recording head 65, and in the illustrated example, is held in a form protruding in the moving path of the recording head 65. Reference numeral 62 denotes a cap on the projection port surface of the recording head 65, which is disposed at a home position adjacent to the blade 61, moves in a direction perpendicular to the moving direction of the recording head 65, contacts the ink ejection port surface, and performs capping. The structure to perform is provided. Further, reference numeral 63 denotes an ink absorber provided adjacent to the blade 61 and, like the blade 61, is held in a form protruding in the moving path of the recording head 65. The blade 61, the cap 62, and the ink absorber 63 constitute a discharge recovery unit 64, and the blade 61 and the ink absorber 63 remove moisture, dust, and the like from the discharge port surface.

  Reference numeral 65 denotes a recording head which has discharge energy generating means and performs recording by discharging ink onto a recording medium facing the discharge port surface where the discharge port is arranged. Reference numeral 66 denotes a movement of the recording head 65 by mounting the recording head 65. It is a carriage for performing. The carriage 66 is slidably engaged with the guide shaft 67, and a part of the carriage 66 is connected to a belt 69 (not shown) driven by a motor 68. As a result, the carriage 66 can move along the guide shaft 67, and the recording area and its adjacent area can be moved by the recording head 65.

  51 is a paper feeding section for inserting a recording medium, and 52 is a paper feed roller driven by a motor (not shown). With these configurations, the recording medium is fed to a position facing the ejection port surface of the recording head 65, and discharged to a paper discharge unit provided with a paper discharge roller 53 as recording progresses. In the above configuration, when the recording head 65 finishes recording and returns to the home position, the cap 62 of the ejection recovery unit 64 is retracted from the moving path of the recording head 65, but the blade 61 protrudes into the moving path. As a result, the ejection port of the recording head 65 is wiped.

  When the cap 62 is in contact with the ejection surface of the recording head 65 to perform capping, the cap 62 moves so as to protrude into the moving path of the recording head. When the recording head 65 moves from the home position to the recording start position, the cap 62 and the blade 61 are at the same position as the above-described wiping position. As a result, the ejection port surface of the recording head 65 is wiped even during this movement. The above-described movement of the recording head 65 to the home position is not only at the end of recording or at the recovery of ejection. While the recording head 65 moves in the recording area for recording, the recording head 65 moves to a home position adjacent to the recording area at a predetermined interval. The wiping is performed with this movement.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. The present invention is not limited by the following examples as long as the gist thereof is not exceeded. Unless otherwise specified, “parts” means “parts by mass” and “%” means “mass%”.

<Example 1>
[Preparation of Pretreatment Solution 1]
First, a pretreatment liquid 1 for treating a fabric with the following formulation was prepared.
・ Acrylate ester resin (solid content 35% emulsion,
Product name: Binder 705 (M); manufactured by Dainichi Seika Co., Ltd. 5 parts Cationic surfactant (solid content 50%,
(Product name: G-50; manufactured by Sanyo Chemical) 1 part, 94 parts of water

[Preparation of pigment ink]
(Pigment dispersion)
Each pigment listed below was dispersed in water together with a polymer dispersant, and a pigment dispersion of each color was prepared according to a conventional method. As the polymer dispersant, a styrene-acrylic acid copolymer (weight average molecular weight 7,000) was used. The formulation of each pigment dispersion was such that the mixing ratio of pigment / polymer dispersant / water was pigment / polymer dispersant / water = 10/3/87 in terms of mass ratio.

(Type of pigment)
Cyan ink: C.I. I. Pigment Blue 15: 1
-Magenta ink: C.I. I. Pigment Red 122
Yellow ink: C.I. I. Pigment Yellow 74
・ Black ink: Carbon black

(Pigment ink)
Using the pigment dispersion of each color obtained above, a pigment ink of each color was prepared according to the following formulation. The viscosity of the obtained pigment ink of each color was about 3 mPa · s to 5 mPa · s.
-60% by mass of the pigment dispersion prepared above
・ Glycerin 5% by mass
・ Diethylene glycol 10% by mass
・ Isopropyl alcohol 10% by mass
・ Water 15% by mass

[Manufacture of printed matter]
A 100% cotton satin woven fabric (a mercerized product) was used as the fabric, and the pretreatment liquid 1 obtained above was applied thereto by a spray method. Next, drying was performed at a drying temperature of 80 ° C. for 3.5 minutes. Thereafter, the pigment ink of each color obtained above was mounted on an ink jet recording apparatus (trade name: BJ F600; manufactured by Canon Inc.), and recording was performed on the fabric to which the pretreatment liquid 1 was applied.

  Next, the post-treatment liquid was applied to the fabric recorded above by a spray method. As the post-treatment liquid, a solution obtained by dissolving 5 parts of sodium di (2-ethylhexyl) sulfosuccinate in 95 parts of water was used. Immediately after the post-treatment, heat fixing was performed for 3.5 minutes at a drying temperature of 150 ° C. using a universal press (HP-B2S; manufactured by Miyata Koki Co., Ltd.). The printed matter obtained as described above was used as the printed matter of Example 1.

<Example 2>
A printed article of Example 2 was produced in the same manner as in Example 1 except that the following self-dispersing pigment having an anionic group was used instead of the pigment dispersion used in Example 1.

(Pigment dispersion)
First, a self-dispersing pigment was prepared by bonding a carboxyl group as an anionic group to the surface of each pigment particle similar to that used in Example 1. Each of the obtained pigments was dispersed in water according to a conventional method to prepare a pigment dispersion of each color used in this example. These pigment dispersions were formulated so that the pigment / water mixing ratio was 10/90 in terms of mass ratio. In each of these pigment dispersions, no dispersant is used.

<Example 3>
A printed material of Example 3 was produced in the same manner as in Example 1 except that the pretreatment liquid 2 prepared below was used instead of the pretreatment liquid 1 in Example 1.

(Pretreatment liquid 2)
Pretreatment liquid 2 was prepared according to the following formulation.
・ Acrylic ester resin emulsion (solid content 35%,
Product name: Binder 705 (M); manufactured by Dainichi Seika) 5 parts Cationic surfactant (solid content 30%,
(Product name: TM-16; manufactured by Sanyo Chemical) 1 part, 94 parts of water

<Example 4>
A printed material of Example 4 was produced in the same manner as in Example 2 except that the pretreatment liquid 2 was used instead of the pretreatment liquid 1 in Example 2.

<Comparative Example 1>
A 100% cotton satin woven fabric (a mercerized product) was used as the fabric, and the pretreatment liquid 1 obtained above was applied to this by a spray method. Next, drying was performed at a drying temperature of 80 ° C. for 3.5 minutes. Thereafter, the pigment ink used in Example 1 was mounted on an ink jet recording apparatus (trade name: BJ F600; manufactured by Canon Inc.), and recording was performed on the fabric to which the pretreatment liquid 1 was applied. Then, without performing post-processing, the printed material of Comparative Example 1 was manufactured by immediately fixing by heating at a drying temperature of 150 ° C. for 3.5 minutes using a universal press (HP-B2S; manufactured by Miyata Koki Co., Ltd.).

<Comparative example 2>
A printed material of Comparative Example 2 was produced in the same manner as Comparative Example 1 except that the pigment ink used in Example 2 was used instead of the pigment ink used in Comparative Example 1.

<Comparative Example 3>
A printed material of Comparative Example 3 was produced in the same manner as Comparative Example 1 except that the pretreatment liquid 2 used in Example 3 was used instead of the pretreatment liquid 1 used in Comparative Example 1.

<Comparative Example 4>
A printed material of Comparative Example 4 was produced in the same manner as Comparative Example 3 except that the pigment ink used in Example 2 was used instead of the pigment ink used in Comparative Example 3.

<Evaluation>
The printed products obtained in Examples 1 to 4 and Comparative Examples 1 to 4 are commercially available acid dyes such as C.I. I. It was immersed in an aqueous solution containing 5% Acid Blue 9 for 10 minutes. Thereafter, these printed products were rinsed for 10 minutes in a household washing machine. Then, the lightness L ₁ ^* satin fabrics not subjected to any processing similar to that used in Examples and Comparative Examples (blank), and chromaticity a ₁ ^* and b ₁ ^*, obtained in Examples or Comparative Examples The lightness L ₂ ^* , chromaticity a ₂ ^* and b ₂ ^{* of} each printed material were measured. A colorimeter (trade name: CM-2022; manufactured by Minolta) was used for color measurement. Color measurement of the lightness L ₂ ^* , chromaticity a ₂ ^*, and b ₂ ^* of each printed product was performed on a portion of the printed product where an image was not formed. The degree of dyeing (ΔE) was calculated from the obtained value using the following formula. Based on the obtained ΔE, the degree of partial dyeing was evaluated according to the following criteria. The evaluation results are shown in Table 1.

(Evaluation criteria)
○: The numerical value (ΔE) is 1 or less and no dyeing is seen. ×: The numerical value (ΔE) is larger than 1 and dyeing is seen.

FIG. 2 is a longitudinal sectional view of a recording head. It is a vertical and horizontal view of a recording head. FIG. 2 is an external perspective view of a recording head in which the recording head shown in FIG. It is a perspective view which shows an example of an inkjet recording device.

Explanation of symbols

13: head 14: nozzle 15: heating element substrate 16: protective layer 17-1, 17-2: electrode 18: heating resistor layer 19: heat storage layer 20: substrate 21: ink 22: ejection orifice (micropore)
23: Meniscus 24: Ink droplet 25: Recording medium 26: Multi nozzle 27: Glass plate 28: Heat generating head 51: Paper feeding unit 52: Paper feed roller 53: Paper discharge roller 61: Blade 62: Cap 63: Ink absorber 64: Ejection recovery unit 65: Recording head 66: Carriage 67: Guide shaft 68: Motor 69: Belt

Claims (8)

In an inkjet textile printing method for performing inkjet recording on a fabric,
A recording step of performing inkjet recording on a fabric containing at least a thermoplastic resin and a nitrogen-containing cationic substance using an ink containing a dispersant and a pigment having an anionic group;
A post-treatment step of imparting an anionic compound that binds to the nitrogen-containing cationic substance to the fabric on which inkjet recording has been performed in the recording step;
And a heating step of heating and fixing the ink of the fabric on which the inkjet recording has been performed, after the post-processing step. In an inkjet textile printing method for performing inkjet recording on a fabric,
A recording step of performing inkjet recording on a fabric containing at least a thermoplastic resin and a nitrogen-containing cationic substance using an ink containing a pigment having an anionic group;
A post-treatment step of imparting an anionic compound that binds to the nitrogen-containing cationic substance to the fabric on which inkjet recording has been performed in the step;
And a heating step of heating and fixing the ink of the fabric on which the inkjet recording has been performed, after the post-processing step.   The ink-jet printing method according to claim 1 or 2, wherein the fabric is treated with a pretreatment liquid having a thermoplastic resin content of 0.5 mass% or more and 7 mass% or less.   The inkjet according to any one of claims 1 to 3, wherein the fabric is treated with a pretreatment liquid having a nitrogen-containing cationic substance content of 0.05% by mass or more and 5% by mass or less. Printing method.   The pretreatment liquid contains at least a thermoplastic resin and a nitrogen-containing cationic substance, and the mass ratio of the content of the thermoplastic resin and the nitrogen-containing cationic substance in the pretreatment liquid is 140: 1 to 1: The inkjet printing method according to claim 3 or 4, which is 10.   The inkjet printing method according to any one of claims 1 to 5, wherein a glass transition temperature of the thermoplastic resin is from -35 ° C to 45 ° C.   The inkjet printing method according to any one of claims 1 to 6, wherein the nitrogen-containing cationic substance is a cationic surfactant.   A printed matter produced by the ink-jet printing method according to any one of claims 1 to 7.

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